Fluorocarbon containing diallylamines

ABSTRACT

Diallyl quaternary ammonium compounds containing a terminal perfluoroisopropoxide group are disclosed. These compounds are useful in monomeric form and especially in polymeric form as oil and water repellents.

United States Patent Boothe et al. [451 July 18, 1972 541 FLUOROCARBONCONTAINING 5s FleldolSearch ..260/89.7,567i6,50I.l5,458, DIALLYLAMINES260/459 [72] Inventors: Jerry E. Boothe Pittsburgh; Mel-win F. 56 m CMHoover, Bethel Park; onu- L; Schlegg, l 9

Pittsburgh, all of Pa. UNITED STATES PATENTS [73] Assignee: CalgouCorporation, Pittsburgh, Pa. 3,288,770 11/1966 Butler ..260/89.7 N X[22] Filed: Nov. 20 1969 3,461,163 8/1969 Boothe ..260/567.6 M

[ 21 Primary Examiner-Leon Zitver Appl. N01: 877,556

' Related U.S. Appllc atloul)nta Division of Ser. No. 786,747, Dec. 24,1968, abandoned.

US. Cl. ..260/567.6 M, 260/86.l N, 260/88.l PN, 260/85.5 AM, 260/89.7 N,260/453 R, 260/456 A, 260/459, 260/482 R, 260/482 C, 260/501. 15,

Assistant Examiner-Michael W. Glynn AttameyWilliam L. Krayer [57]ABSTRACT Diallyl quaternary ammonium compounds containing a ter-3Clllms,NoDrawlngs FLUOROCARBON CONTAINING DIALLYLAMINES This case is adivision of application, Ser. No. 786,747, filed Dec. 24, 1968 nowabandoned.

BACKGROUND OF THE INVENTION This invention relates to novel diallylquaternary ammonium compounds containing a terminalperfluoroisopropoxide group and polymers thereof.

This invention further relates to the treatment of fibrous materials,especially textiles, with the compounds of this invention to impart tosuch fibers oil and water repellency characteristics.

Many types of fluorinated compositions had been proposed and used in thepast for oil and water repellency. See, for example, U.S. Pat. Nos.3,336,157; 3,293,306; 3,207,730. There are many others. Most suchdisclosures which are directed particularly to polymers containingfluorinated (or perfluoro) groups are constructed from monoethylenicallyunsaturated monomers such as acrylic or vinyl monomers.

The polymerization mechanism of diallyl ammonium monomers is describedin an article by Butler and Angelo, J.A.C.S. 79 3128 (1957). See alsoU.S. Pat. No. 3,288,770. They may be copolymerized with certain acrylicmonomers as in U.S. Pat. No. 2,923,701, and with sulfur dioxide as inI-Iarada and Katayama, U.S. Pat. No. 3,375,233. Certain fluorinatedamines have also formed polymers with sulfur dioxide as in Wright andFriedlanders U.S. Pat. No. 3,072,616.

The majority of fluorinated compositions have a fluorinated carbon chainof at least four carbons terminated by a CF group. Most of therepellency properties of such compounds are provided by the terminal CFThe trifluoro methyl group lowers the critical surface tension at theair-fiber interface. A perfluoroisopropoxide group contains two CFgroups. It has a greater percentage of its fluorine atoms incorporatedin the lower energy -CF groups. Therefore a compound containing aterminal perfluoroisopropoxide group would have a low critical surfacetension value and good repellency characteristics.

Perfluoroisopropyl groups have been successfully incorporated intopolymers. For example, see U.S. Pat. No. 3,361,685 where Pittmandiscloses glycidyl ethers and polymers thereof which contain terminalperfluoroisopropyl groups. See also Pittman U.S. Pat. No. 3,382,222which discloses allyl ethers and polymers thereof containing a terminalperfluoroisopropyl group. The wetting characteristics of these groupsare described by Pittman, Sharp and Ludwig in the Journal of PolymerScience, Volume 6, Part A-l, l,729-1,751

SUMMARY OF THE INVENTION We have invented a series of fluorinecompositions which are different from compositions of the prior art.They are quaternary ammonium compounds containing two allyl groups andat least one terminal perfluoroisopropoxide group.

Our novel compositions are compounds of the formula where R, is abridging group selected from the group consisting of where n is aninteger from 1 to 8 and R is selected from the group consisting of H andalkyl and alkanol groups of from one to four carbon atoms; R- isselected from the group consisting of H, R,OCF(CF and alkyl and alkanolgroups having from one to four carbon atoms; Xis an anion selected fromthe group consisting of P C1 B1 F CH SO,,Q and cn,coo.

We have found that such compounds having two allyl groups attached tothe nitrogen may be polymerized into high molecular weight linearpolymers in a manner similar to that disclosed by Butler in U.S. Pat.No. 3,288,770. They also form high molecular weight products bycopolymerization with compounds of the type used by Butler, that is,dialkyl diallyl ammonium compounds.

The compounds of our invention may be copolymerized with monomers whichare well known and used in the art of repellency finishes. Examples ofthese are the diethylenically unsaturated monomers such as butadiene,isoprene, and chloroprene. Some examples of useful monoethylenicallyunsaturated monomers are diacetone acrylamide, styrene, acrylonitrile,and lower alkyl acrylates containing alkyl groups of from one to 10carbon atoms.

The monomers of our invention may be made by the syntheses indicated.

' ea [(0 F920 F O CHzCH OHCH2N(CH3) 0mcr1=cnm1 ol Specific examples ofthe syntheses are EXAMPLEIV e3 [(6 F920 F0 (CH2)5N(CH3) (CH2CH=CH2):] Dr

To a 2-liter steel cylinder was added 58 g. (1.0 mole) of dry KF. Thecylinder was fitted with a pressure gauge and valve, evacuated, and 116g. (1.0 mole) of hexafluoroacetone and 618 g. of CI-I,CN was added. Themixture was mixed by shaking for 0.5 hours and 1,150 g. (5.0 moles) of1,5-dibromopentane was added. The reaction mixture was heated at for 72hours, then distilled yielding 269 g. of (CF ),CFO(CH ),Br, b.p.94-96/42 mm. This compound was then analyzed for percentC, H, Br and F.

Theoretical: C=28.6%; I-I=3.0%; Br=23.9%; F=39.7% Actual: C=28.7%;H=2.9%; Br-24.0%; F=39.8%

To a ZOO-ml. Pyrex resin flask was added 49.6 g. (0.15 mole) of (CF),CFO(Cl-l Br and 94.1 g. (0.85 mole) of CH N(CH Cl-l CH The mixture washeated at 112 for 18 hours and after removing unreacted startingmaterials under vacuum 58 g. of solid (CF CFO(CH N(CH (CH Cl-l CH B1 wasobtained.

EXAMPLE V Similar to Example IV, (CFQ CFOK and 1,4-dibromobutane wereheated to 80 in CH CN for 80 hours, then distilled yielding (CF CFO(CHBr,b.p. 87l55 mm.

Reaction of (CF CFO(Cl-l Br with CH N(Cl-l Cl-l CH yielded Thecompositions of our invention may be used for repellency in themonomeric form or polymeric form. We have homopolymerized the compoundsof our invention. An example of the polymerization is set forth in thefollowing:

EXAMPLE VI 6 Homopolymerlzation 01' (CFmC F O(CH1)4I T(CH;) (CH2CH=CH)zBr Seventy-five grams of a 40 percent monomer solution (30 gm. ofactive monomer, 0.0695 moles) was placed in a 250 ml reaction flask. Thesolution was purged for 1 hour at 25 C. and the temperature raised to 80C. Ammonium persulfate catalyst was introduced at a rate of 0.1 molescatalyst per mole monomer per minute for a period of 1 hour. Thecatalyst addition was then terminated and the reaction mixture held at94 C. for 1 hour. The reaction mixture was then cooled to roomtemperature and the polymer isolated.

The compounds of our invention can be applied to the fiber by means suchas padding. Application can also be accomplished by dipping, spraying,and other methods used in the art. The compounds can be applied fromdispersions, emulsions or solutions depending on the applicationtechniques used. The compounds of our invention can be formulated withfluorocarbon extenders such as Phobetex.

The necessary amount of compound add-on (weight of dry compound on fiberor percent WOF) is difficult to ascertain. This amount depends on suchfactors as the repellency properties desired in finished product. Thecompounds of our invention are effective over a wide range of add-ons.However the optimum conditions are achieved with add-ons between 0.5percent and 10 percent by weight of dry compound on fiber.

The polymers of our invention have a wide range of composition. Thecomposition is determined by the desired oil and water repellencyproperties which are to be imparted to the fiber. In many cases only asmall weight percent of fluorinated group is necessary to achievemeasurable repellency properties. However we have found that the polymershould contain at least 5 percent by weight units of the fluorinatedgroup to impart a practical oil and water repellency to most fibers. Theremainder of the polymer composition consists of comonomers which arewell known and used in the art of where R, is a bridging group selectedfrom the group consisting of where n is an integer from 1 to 8; R" isselected from the group consisting of hydrogen and alkyl groups of oneto four carbon atoms; X" is an anion selected from the group consistingof F CE, Br l CH SO and CH COO 2. Compound of claim 1 where R is R is CHand X is C1 3. Compound of claim 1 where R is 4- CH where n is aninteger from 1 to 5; R is CH and X" is CB.

2. Compound of claim 1 where R1 is R is CH3 and X is Cl .
 3. Compound ofclaim 1 where R1 is - CH2 -n where n is an integer from 1 to 5; R is CH3and ''''X'''' is Cl .